EP0005251B1 - Process for the preparation of sulfinates of 4,4'-diaminobenzhydrol and of its substituted products, and copying paper containing these compounds - Google Patents
Process for the preparation of sulfinates of 4,4'-diaminobenzhydrol and of its substituted products, and copying paper containing these compounds Download PDFInfo
- Publication number
- EP0005251B1 EP0005251B1 EP79101293A EP79101293A EP0005251B1 EP 0005251 B1 EP0005251 B1 EP 0005251B1 EP 79101293 A EP79101293 A EP 79101293A EP 79101293 A EP79101293 A EP 79101293A EP 0005251 B1 EP0005251 B1 EP 0005251B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- optionally substituted
- general formula
- sulphinates
- organic solvents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 title claims description 7
- MABRBBOPUASAAI-UHFFFAOYSA-N bis(4-aminophenyl)methanol Chemical compound C1=CC(N)=CC=C1C(O)C1=CC=C(N)C=C1 MABRBBOPUASAAI-UHFFFAOYSA-N 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- -1 alkali metal salts Chemical class 0.000 claims description 36
- 150000003254 radicals Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical group 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- RJSYPKWVIJGNLO-UHFFFAOYSA-N CCOClOC Chemical compound CCOClOC RJSYPKWVIJGNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- YLZSIUVOIFJGQZ-UHFFFAOYSA-N bis[4-(dimethylamino)phenyl]methanol Chemical compound C1=CC(N(C)C)=CC=C1C(O)C1=CC=C(N(C)C)C=C1 YLZSIUVOIFJGQZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 6
- FXJVNINSOKCNJP-UHFFFAOYSA-M 4-methylbenzenesulfinate Chemical compound CC1=CC=C(S([O-])=O)C=C1 FXJVNINSOKCNJP-UHFFFAOYSA-M 0.000 description 6
- FBEHFRAORPEGFH-UHFFFAOYSA-N Allyxycarb Chemical compound CNC(=O)OC1=CC(C)=C(N(CC=C)CC=C)C(C)=C1 FBEHFRAORPEGFH-UHFFFAOYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- YZGQDNOIGFBYKF-UHFFFAOYSA-N Ethoxyacetic acid Chemical compound CCOCC(O)=O YZGQDNOIGFBYKF-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 150000003455 sulfinic acids Chemical class 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KYAJBRQELLCANX-UHFFFAOYSA-N acetic acid acetylene Chemical group C#C.CC(O)=O KYAJBRQELLCANX-UHFFFAOYSA-N 0.000 description 2
- AZZGCPLRBXAOCT-UHFFFAOYSA-N acetic acid;acetylene Chemical compound C#C.CC(O)=O.CC(O)=O AZZGCPLRBXAOCT-UHFFFAOYSA-N 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-M benzenesulfinate Chemical compound [O-]S(=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-M 0.000 description 2
- HEBCMOUTQXRNMH-UHFFFAOYSA-N bis(4-morpholin-4-ylphenyl)methanol Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(O)C(C=C1)=CC=C1N1CCOCC1 HEBCMOUTQXRNMH-UHFFFAOYSA-N 0.000 description 2
- VPFVXCZLOJXWNB-UHFFFAOYSA-N bis(4-piperidin-1-ylphenyl)methanol Chemical compound C=1C=C(N2CCCCC2)C=CC=1C(O)C(C=C1)=CC=C1N1CCCCC1 VPFVXCZLOJXWNB-UHFFFAOYSA-N 0.000 description 2
- KROZDCJSEHBOAS-UHFFFAOYSA-N bis[4-(2-phenylethylamino)phenyl]methanol Chemical compound C=1C=C(NCCC=2C=CC=CC=2)C=CC=1C(O)C(C=C1)=CC=C1NCCC1=CC=CC=C1 KROZDCJSEHBOAS-UHFFFAOYSA-N 0.000 description 2
- HHSQBPWHSMRTNU-UHFFFAOYSA-N bis[4-(benzylamino)phenyl]methanol Chemical compound C=1C=C(NCC=2C=CC=CC=2)C=CC=1C(O)C(C=C1)=CC=C1NCC1=CC=CC=C1 HHSQBPWHSMRTNU-UHFFFAOYSA-N 0.000 description 2
- DWHFBLIWMWWWCC-UHFFFAOYSA-N bis[4-(dibenzylamino)phenyl]methanol Chemical compound C=1C=C(N(CC=2C=CC=CC=2)CC=2C=CC=CC=2)C=CC=1C(O)C(C=C1)=CC=C1N(CC=1C=CC=CC=1)CC1=CC=CC=C1 DWHFBLIWMWWWCC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XNEFVTBPCXGIRX-UHFFFAOYSA-M methanesulfinate Chemical compound CS([O-])=O XNEFVTBPCXGIRX-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- VMHBLCOVWRALQY-UHFFFAOYSA-N (4-chlorophenyl)methanesulfinic acid Chemical compound OS(=O)CC1=CC=C(Cl)C=C1 VMHBLCOVWRALQY-UHFFFAOYSA-N 0.000 description 1
- HEHLOWOOVUULKX-UHFFFAOYSA-N (4-methylphenyl)methanesulfinic acid Chemical compound CC1=CC=C(CS(O)=O)C=C1 HEHLOWOOVUULKX-UHFFFAOYSA-N 0.000 description 1
- ZDOWGOCJXFRDOM-UHFFFAOYSA-N 1,2-dimethyl-2,3-dihydroindole Chemical compound C1=CC=C2N(C)C(C)CC2=C1 ZDOWGOCJXFRDOM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- SNECTTSOTKJYID-UHFFFAOYSA-N 1-(4-aminophenyl)-1-(4-amino-2,3,5-triethylphenyl)propan-1-ol Chemical compound C(C)C=1C(=C(C(=C(C(C2=CC=C(C=C2)N)(O)CC)C1)CC)CC)N SNECTTSOTKJYID-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- PQMWKAXQYMNZOD-UHFFFAOYSA-N 1-methyl-3,4,4a,5-tetrahydro-2h-quinoline Chemical compound C1C=CC=C2N(C)CCCC21 PQMWKAXQYMNZOD-UHFFFAOYSA-N 0.000 description 1
- UCUBNBPADCWTMC-UHFFFAOYSA-N 1-methyl-6-[(1-methyl-3,4,4a,5-tetrahydro-2H-quinolin-6-yl)methyl]-3,4,4a,5-tetrahydro-2H-quinoline Chemical compound CN1CCCC2CC(=CC=C12)CC=1CC2CCCN(C2=CC=1)C UCUBNBPADCWTMC-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- VLUWLNIMIAFOSY-UHFFFAOYSA-N 2-methylbenzenesulfinic acid Chemical compound CC1=CC=CC=C1S(O)=O VLUWLNIMIAFOSY-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical compound CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 description 1
- YDQNDKBOOVXRTL-UHFFFAOYSA-N 4-acetamidobenzenesulfinic acid Chemical compound CC(=O)NC1=CC=C(S(O)=O)C=C1 YDQNDKBOOVXRTL-UHFFFAOYSA-N 0.000 description 1
- AOQYAMDZQAEDLO-UHFFFAOYSA-M 4-chlorobenzenesulfinate Chemical compound [O-]S(=O)C1=CC=C(Cl)C=C1 AOQYAMDZQAEDLO-UHFFFAOYSA-M 0.000 description 1
- POLIJPSTOUXTJG-UHFFFAOYSA-N 4-ethoxybenzenesulfinic acid Chemical compound CCOC1=CC=C(S(O)=O)C=C1 POLIJPSTOUXTJG-UHFFFAOYSA-N 0.000 description 1
- DBWIXIGUNHMVPO-UHFFFAOYSA-N 4-ethylbenzenesulfinic acid Chemical compound CCC1=CC=C(S(O)=O)C=C1 DBWIXIGUNHMVPO-UHFFFAOYSA-N 0.000 description 1
- YVZWQPOTHRMEQW-UHFFFAOYSA-N 4-methoxybenzenesulfinic acid Chemical compound COC1=CC=C(S(O)=O)C=C1 YVZWQPOTHRMEQW-UHFFFAOYSA-N 0.000 description 1
- FXJVNINSOKCNJP-UHFFFAOYSA-N 4-methylbenzenesulfinic acid Chemical compound CC1=CC=C(S(O)=O)C=C1 FXJVNINSOKCNJP-UHFFFAOYSA-N 0.000 description 1
- QCCKSFHMARIKSK-UHFFFAOYSA-N 5,6-dihydro-4h-pyrrolo[3,2,1-ij]quinoline Chemical compound C1CCC2=CC=CC3=C2N1C=C3 QCCKSFHMARIKSK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RWLVYSUALAOEHD-UHFFFAOYSA-N C1=CC=C(C=C1)CCCNC2=CC=C(C=C2)C(C3=CC=C(C=C3)NCCCC4=CC=CC=C4)O Chemical compound C1=CC=C(C=C1)CCCNC2=CC=C(C=C2)C(C3=CC=C(C=C3)NCCCC4=CC=CC=C4)O RWLVYSUALAOEHD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NVSONFIVLCXXDH-UHFFFAOYSA-N benzylsulfinic acid Chemical compound O[S@@](=O)CC1=CC=CC=C1 NVSONFIVLCXXDH-UHFFFAOYSA-N 0.000 description 1
- VLVCQMHBBRHBLW-UHFFFAOYSA-N bis(1-methyl-3,4,4a,5-tetrahydro-2h-quinolin-6-yl)methanol Chemical compound C=1C=C2N(C)CCCC2CC=1C(O)C(C1)=CC=C2C1CCCN2C VLVCQMHBBRHBLW-UHFFFAOYSA-N 0.000 description 1
- DCBILZQETXFXAY-UHFFFAOYSA-N butane-1-sulfinic acid Chemical compound CCCCS(O)=O DCBILZQETXFXAY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- CPGLZCPYWQALMI-UHFFFAOYSA-N dodecane-1-sulfinic acid Chemical compound CCCCCCCCCCCCS(O)=O CPGLZCPYWQALMI-UHFFFAOYSA-N 0.000 description 1
- RQIFXTOWUNAUJC-UHFFFAOYSA-N ethanesulfinic acid Chemical compound CCS(O)=O RQIFXTOWUNAUJC-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- DZFWNZJKBJOGFQ-UHFFFAOYSA-N julolidine Chemical compound C1CCC2=CC=CC3=C2N1CCC3 DZFWNZJKBJOGFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- XNEFVTBPCXGIRX-UHFFFAOYSA-N methanesulfinic acid Chemical compound CS(O)=O XNEFVTBPCXGIRX-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- YGUNSCNKBIOMSG-UHFFFAOYSA-N propane-1-sulfinic acid Chemical compound CCCS(O)=O YGUNSCNKBIOMSG-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036633 rest Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- JFXAUUFCZJYLJF-UHFFFAOYSA-M sodium;4-chlorobenzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=C(Cl)C=C1 JFXAUUFCZJYLJF-UHFFFAOYSA-M 0.000 description 1
- LYPGDCWPTHTUDO-UHFFFAOYSA-M sodium;methanesulfinate Chemical compound [Na+].CS([O-])=O LYPGDCWPTHTUDO-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
Definitions
- the alkyl radicals mentioned in the formulas (I) and (11) are generally those having 1-6 C atoms.
- the alkyl radicals mentioned under D can have up to 20 carbon atoms.
- Particularly suitable substituents of the alkyl radicals are, for example, halogen, hydroxy, C 1 -C 4 alkoxy or cyano.
- Aryl is preferably understood to mean phenyl or 1- or 2-naphthyl and aralkyl is benzyl and ⁇ -phenyl-C 1 -C 4 -alkyl.
- the phenyl rings can be substituted, for example, by 1-4 radicals such as halogen, C 1 -C 4 alkyl, hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, carboxyl, amidocarbonyl, cyano, nitro, amidosulfonyl, C 1 -C 3 alkylcarbonylamino or benzoylamino.
- Cycloalkyl is especially cyclopentyl and cyclohexyl, e.g. can be substituted by 1-4 radicals, in particular methyl.
- heterocyclic rings which are formed by R 1 and R 2 or by R 3 and R 4 with the adjacent nitrogen atom are the piperidine, N-methylpiperazine and the morpholine ring.
- heterocyclic rings which are formed by R 1 and / or R 2 being bound to the aromatic radical A or by R 3 and / or R 4 being bound to the aromatic radical B are julolidine, lilolidine, N- Methyltetrahydroquinoline and 1,2-dimethylindoline called.
- a and B preferably represent a 1,4-phenylene or 1,4-naphthylene radical. These radicals can be substituted by 1-4 substituents such as C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen.
- Halogen is understood to mean in particular fluorine, chlorine and bromine.
- Suitable hetaryl residues D are e.g. the quinoline (5), quinoline (6) and indazole (7) residues.
- the process according to the invention is very particularly suitable for the production of sulfinates of Michler's hydrol (4,4'-tetramethyldiaminobenzhydrol).
- Suitable solvents are monohydric and polyhydric alcohols, and also their ethers, for example methanol, ethanol, propanol, methyl glycol, ethyl glycol, butyl glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol, methyl glycol acetate, ethylene glycol nitrile diacetate, ethylene glycol nitrile diacetate, and ethylene glycol nitrile diacetate, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, acetylene glycol acetylene diacetate, acetylene glycol acetylene di
- Suitable starting materials of the general formula are: 4,4'-diaminobenzhydro !, 4,4'-tetramethyldiaminobenzhydrol, 4,4'-tetraethyldiaminobenzhydrol, 4,4'-tetramethyldiamino-2,2'-dimethoxybenzhydrol, 4,4'-tetramethyldia- mino-2,2'-dimethylbenzhydrol, 4,4'-Bisbenzylmethylaminobenzhydrol, 4,4'-Bisbenzyläthylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4 '-bis- phenyläthylaminobenzhydrol, 4,4' -Bisäthyloxäthylaminobenzhydrol, 4,4'-Tetrachloräthyldiaminobenzhydr
- Suitable low-molecular organic mono- or dicarboxylic acids are formic acid, acetic acid, propionic acid, glycolic acid, methoxyacetic acid, ethoxyacetic acid, oxalic acid, maleic acid and succinic acid. Acetic acid is preferred among these carboxylic acids.
- Suitable sulfinic acids of the formula 111 are, for example, methanesulfinic acid, ethanesulfinic acid, propanesulfinic acid, butanesulfinic acid, decanesulfinic acid, dodecanesulfinic acid, octadecansulfinic acid, benzylsulfinic acid, 4-methylbenzylsulfinic acid, 4-chlorobenzylsulfinic acid, cyclohexylsulfinsulfonic acid, 2-chlorobenzene acid, benzene , 2-methylbenzenesulfinic acid, 4-ethylbenzenesulfinic acid, 4-methoxybenzenesulfinic acid, 4-ethoxybenzenesulfinic acid and 4-acetylaminobenzenesulfinic acid.
- 4-methylbenzenesulfinic acid is particularly preferred.
- the reaction can be carried out at a temperature of 20-100 °
- Suitable solvents are: methanol, isopropanol, ethylene glycol, methyl glycol, ethyl glycol, butyl glycol, methyl glycol acetate, ethylene glycol diacetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dioxane, tetrahydrofuran and acetonitrile.
- Lactic acid can be used instead of glycolic acid with the same good result.
- Michler's hydrol 85 g of Michler's hydrol are dissolved in a mixture of 50 ml of formic acid and 200 ml of ethanol and 50.8 g of sodium p-toluenesulfinate are added. After 10 minutes the sulfinate of Michler's hydrol crystallizes out. The suspension is allowed to stir for 4 hours at room temperature, is filtered off with suction and the reaction product is washed in small portions with 400 ml of alcohol until the filtrate is light, then with 0.5 l of a 1% aqueous sodium sulfinate solution.
- Suitable hydroles are: 4,4'-tetramethyldiamino-2,2'-dimethoxybenzhydrol, 4,4'-tetramethyl-diamino-2,2'-dimethylbenzhydrol, 4,4'-bisbenzylmethylaminobenzhydrol, 4,4'-bisbenzylethylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4 '-Bisphenylvesthylaminobenzhydrol, 4,4' -bis- äthyloxäthylaminobenzhydrol, 4,4'-Bischloräthyl- äthylaminobenzhydrol, 4,4'-Bispiperidinobenzhydrol, 4,4 ' -Bismorpholinobenzhydrol, 4,4 ' -Bismorpholinobenzhydrol, 4,4 ' -Bis-
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Color Printing (AREA)
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Sulfinaten der allgemeinen Formel
- A und B unabhängig voneinander einen gegebenenfalls substituierten 1,4-Arylenrest und R1' R2, R3 und R4 unabhängig voneinander Wasserstoff oder einen gegebenenfalls substituierten Alkyl-, Cycloalkyl-, Aralkyl- oder Arylrest bedeuten, oder
- R1 und R2 bzw. R3 und R4 gemeinsam mit dem benachbarten Stickstoffatom einen heterocyclischen Ring bilden, oder
einer oder mehrere der Reste - R1' R2, R3 und R4mit dem Stickstoff und einem benachbarten Kohlenstoffatom des Restes A bzw. B einen heterocyclischen Ring bilden, und D für einen gegebenenfalls substituierten Alkyl-, Aryl-, Aralkyl-, Cycloalkyl- oder Hetarylrest steht. durch Umsetzung von 4,4'-Diaminobenzhydrolen der allgemeinen Formel
- in welcher die Reste R1' R2, R3, R4, A und B die gleiche Bedeutung wie in Formel I haben, mit Verbindungen der Formel
- in welcher der Rest D die gleiche Bedeutung wie in Formel hat, oder deren Alkali- bzw. Erdalkalisalzen unter wasserfreien Bedingungen in aliphatischen Mono- oder Dicarbonsäuren und gegebenenfalls anderen organischen Lösungsmitteln, dadurch gekennzeichnet, dass die Sulfinate durch Verdünnen mit wasserfreien organischen Lösungsmitteln ausgefällt werden.
- A and B independently of one another represent an optionally substituted 1,4-arylene radical and R 1 ' R 2 , R 3 and R 4 independently of one another are hydrogen or an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical, or
- R 1 and R 2 or R 3 and R 4 together with the adjacent nitrogen atom form a heterocyclic ring, or
one or more of the residues - R 1 ' R 2 , R 3 and R 4 form a heterocyclic ring with the nitrogen and an adjacent carbon atom of the radicals A and B, and D represents an optionally substituted alkyl, aryl, aralkyl, cycloalkyl or hetaryl radical. by reacting 4,4'-diaminobenzhydroles of the general formula
- in which the radicals R 1 ' R 2 , R 3 , R 4 , A and B have the same meaning as in formula I, with compounds of the formula
- in which the radical D has the same meaning as in formula, or the alkali metal or alkaline earth metal salts thereof under anhydrous conditions in aliphatic mono- or dicarboxylic acids and optionally other organic solvents, characterized in that the sulfinates are precipitated by dilution with anhydrous organic solvents.
Die in den Formeln (I) und (11) genannten Alkylreste sind im allgemeinen solche mit 1-6 C-Atomen. Die unter D genannten Alkylreste können bis zu 20 C-Atome haben. Besonders geeignete Substituenten der Alkylreste sind beispielsweise Halogen, Hydroxy, C1-C4-Alkoxy oder Cyan.The alkyl radicals mentioned in the formulas (I) and (11) are generally those having 1-6 C atoms. The alkyl radicals mentioned under D can have up to 20 carbon atoms. Particularly suitable substituents of the alkyl radicals are, for example, halogen, hydroxy, C 1 -C 4 alkoxy or cyano.
Unter Aryl wird vorzugsweise Phenyl oder 1-oder 2-Naphthyl und unter Aralkyl Benzyl und β-Phenyl-C1-C4-alkyl verstanden. Die Phenylringe können durch beispielsweise 1-4 Reste wie Halogen, C1-C4-Alkyl, Hydroxy, C1-C4-Alkoxy, C1-C4 - Alkoxycarbonyl, Carboxyl, Amidocarbonyl, Cyan, Nitro, Amidosulfonyl, C1-C3-Alkylcarbonylamino oder Benzoylamino substituiert sein.Aryl is preferably understood to mean phenyl or 1- or 2-naphthyl and aralkyl is benzyl and β-phenyl-C 1 -C 4 -alkyl. The phenyl rings can be substituted, for example, by 1-4 radicals such as halogen, C 1 -C 4 alkyl, hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, carboxyl, amidocarbonyl, cyano, nitro, amidosulfonyl, C 1 -C 3 alkylcarbonylamino or benzoylamino.
Cycloalkyl steht insbesondere für Cyclopentyl und Cyclohexyl, die z.B. durch 1-4 Reste, insbesondere Methyl substituiert sein können.Cycloalkyl is especially cyclopentyl and cyclohexyl, e.g. can be substituted by 1-4 radicals, in particular methyl.
Als Beispiele von heterocyclischen Ringen, welche durch R1 und R2 oder durch R3 und R4 mit dem benachbarten Stickstoffatom gebildet werden, seien der Piperidin-, N-Methylpiperazin- und der Morpholinring genannt. Als Beispiele von heterocyclischen Ringen, welche dadurch gebildet werden, dass R1 und/oder R2 an den aromatischen Rest A oder dadurch, dass R3 und/oder R4 an den aromatischen Rest B gebunden sind, seien Julolidin, Lilolidin, N-Methyltetrahydrochinolin und 1,2-Dimethylindolin genannt.Examples of heterocyclic rings which are formed by R 1 and R 2 or by R 3 and R 4 with the adjacent nitrogen atom are the piperidine, N-methylpiperazine and the morpholine ring. Examples of heterocyclic rings which are formed by R 1 and / or R 2 being bound to the aromatic radical A or by R 3 and / or R 4 being bound to the aromatic radical B are julolidine, lilolidine, N- Methyltetrahydroquinoline and 1,2-dimethylindoline called.
A und B stehen vorzugsweise für einen 1,4-Phenylen- oder 1,4-Naphthylen-Rest. Diese Reste können durch 1-4 Substituenten wie C1-C4-Alkyl, Cl-C4-Alkoxy oder Halogen substituiert sein.A and B preferably represent a 1,4-phenylene or 1,4-naphthylene radical. These radicals can be substituted by 1-4 substituents such as C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen.
Unter Halogen wird insbesondere Fluor, Chlor und Brom verstanden.Halogen is understood to mean in particular fluorine, chlorine and bromine.
Geeignete Hetarylreste D sind z.B. der Chinolin-(5)-, Chinolin-(6)- und Indazol-(7)-Rest.Suitable hetaryl residues D are e.g. the quinoline (5), quinoline (6) and indazole (7) residues.
Eine bevorzugte Verfahrensweise besteht darin, dass man 4,4' -Diaminobenzhydrole der allgemeinen Formel
- R5, R6, R7 und Ra unabhängig voneinander für Wasserstoff oder einen Alkylrest mit 1-4 Kohlenstoffatomen stehen, und
- Rg und R10 unabhängig voneinander Wasserstoff, Methyl, Äthyl, Methoxy, Äthoxy, Chlor oder Brom bedeuten, mit Verbindungen der Formel
- R für gegebenenfalls durch Halogen substituiertes Alkyl mit 1-18 Kohlenstoffatomen oder für gegebenenfalls durch Halogen, Methyl, Äthyl, Hydroxy, Methoxy, Äthoxy, Nitro, Carboxyl oder Acetylamino substituiertes Phenyl steht, und Alkyl vorzugsweise durch 1 dieser Reste und Phenyl durch 1 oder 2 dieser Reste substituiert sein können,
- oder deren Alkalimetallsalzen in Gegenwart von aliphatischen Monocarbonsäuren und gegebenenfalls anderen organischen Lösungsmitteln unter Ausschluss von Wasser zu Verbindungen der Formel
- umsetzt, und die Verbindungen (VI) durch Verdünnen mit wasserfreien organischen Lösungsmitteln ausfällt.
- R 5 , R 6 , R 7 and Ra independently of one another represent hydrogen or an alkyl radical having 1-4 carbon atoms, and
- Rg and R 10 are independently hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine or bromine, with compounds of the formula
- R represents alkyl optionally substituted by halogen with 1-18 carbon atoms or phenyl optionally substituted by halogen, methyl, ethyl, hydroxy, methoxy, ethoxy, nitro, carboxyl or acetylamino, and alkyl preferably by 1 of these radicals and phenyl by 1 or 2 these radicals can be substituted,
- or their alkali metal salts in the presence of aliphatic monocarboxylic acids and optionally other organic solvents with the exclusion of water to give compounds of the formula
- converts, and the compounds (VI) precipitates by dilution with anhydrous organic solvents.
Das erfindungsgemässe Verfahren ist ganz besonders geeignet zur Herstellung von Sulfinaten des Michlers Hydrol (4,4'-Tetramethyldiaminobenzhydrol).The process according to the invention is very particularly suitable for the production of sulfinates of Michler's hydrol (4,4'-tetramethyldiaminobenzhydrol).
Als Lösungsmittel eignen sich ein- und mehrwertige Alkohole, sowie deren Äther, beispielsweise Methanol, Äthanol, Propanol, Methylglykol, Äthylglykol, Butylglykol, Äthylenglykoldimethyläther, Äthylenglykoldiäthyläther, Diäthylenglykoldimethyläther, Äthylenglykol, Methylglykolacetat, Äthylenglykoldiacetat, Acetonitril, Tetrahydrofuran und Dioxan.Suitable solvents are monohydric and polyhydric alcohols, and also their ethers, for example methanol, ethanol, propanol, methyl glycol, ethyl glycol, butyl glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol, methyl glycol acetate, ethylene glycol nitrile diacetate, ethylene glycol nitrile diacetate, and ethylene glycol nitrile diacetate, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, acetylene glycol acetylene diacetate, acetylene glycol acetylene diacetate, acetic acid acetylene glycol acetic acid, acetylene glycol acetylene acetic acid, acetylene glycol acetylene acetylene, acetylene glycol acetic acid,
Geeignete Ausgangsmaterialien der allgemeinen Formel sind: 4,4'-Diaminobenzhydro!, 4,4'-Tetramethyldiaminobenzhydrol, 4,4'-Tetraäthyldiaminobenzhydrol, 4,4'-Tetramethyldiamino-2,2'-dimethoxybenzhydrol, 4,4'-Tetramethyldia- mino-2,2'-dimethylbenzhydrol, 4,4'-Bisbenzylmethylaminobenzhydrol, 4,4'-Bisbenzyläthylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4'-Bis- phenyläthylaminobenzhydrol, 4,4'-Bisäthyloxäthylaminobenzhydrol, 4,4'-Tetrachloräthyldiaminobenzhydrol, 4,4'-Bispiperidinobenzhydrol, 4,4'-Bismorpholinobenzhydrol, 4,4'-Bis-N-methylpiperazinobenzhydrol, Bis-(N-methyl-6-tetrahydrochinolyl)-methanol.Suitable starting materials of the general formula are: 4,4'-diaminobenzhydro !, 4,4'-tetramethyldiaminobenzhydrol, 4,4'-tetraethyldiaminobenzhydrol, 4,4'-tetramethyldiamino-2,2'-dimethoxybenzhydrol, 4,4'-tetramethyldia- mino-2,2'-dimethylbenzhydrol, 4,4'-Bisbenzylmethylaminobenzhydrol, 4,4'-Bisbenzyläthylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4 '-bis- phenyläthylaminobenzhydrol, 4,4' -Bisäthyloxäthylaminobenzhydrol, 4,4'-Tetrachloräthyldiaminobenzhydrol, 4,4'-Bispiperidinobenzhydrol, 4,4'-Bismorpholinobenzhydrol, 4,4'-Bis-N-methylpiperazinobenzhydrol, Bis- (N-methyl-6-tetrahydroquinolyl) -methanol.
Als niedermolekulare organische Mono- bzw. Dicarbonsäuren eignen sich beispielsweise Ameisensäure, Essigsäure, Propionsäure, Glykolsäure, Methoxyessigsäure, Äthoxyessigsäure, Oxalsäure, Maleinsäure und Bernsteinsäure. Bevorzugt unter diesen Carbonsäuren ist die Essigsäure.Examples of suitable low-molecular organic mono- or dicarboxylic acids are formic acid, acetic acid, propionic acid, glycolic acid, methoxyacetic acid, ethoxyacetic acid, oxalic acid, maleic acid and succinic acid. Acetic acid is preferred among these carboxylic acids.
Geeignete Sulfinsäuren der Formel 111 sind beispielsweise Methansulfinsäure, Äthansulfinsäure, Propansulfinsäure, Butansulfinsäure, Decansulfinsäure, Dodecansulfinsäure, Octadecansulfinsäure, Benzylsulfinsäure, 4-Methylbenzylsulfinsäure, 4-Chlorbenzylsulfinsäure, Cyclohexylsulfinsäure, Benzolsulfinsäure, 2-Chlorbenzolsulfinsäure, 3-Chlorbenzolsulfinsäure, 4-Chlorbenzolsulfinsäure, 4-Brombenzolsulfinsäure, 2-Methylbenzolsulfinsäure, 4-Äthylbenzolsulfinsäure, 4-Methoxybenzolsulfinsäure, 4-Äthoxybenzolsulfinsäure und 4-Acetylaminobenzolsulfinsäure. Unter diesen Sulfinsäuren ist die 4-Methylbenzolsulfinsäure besonders bevorzugt. Die Umsetzung kann bei einer Temperatur von 20-100°C durchgeführt werden, der bevorzugte Temperaturbereich liegt bei 20-40°C.Suitable sulfinic acids of the formula 111 are, for example, methanesulfinic acid, ethanesulfinic acid, propanesulfinic acid, butanesulfinic acid, decanesulfinic acid, dodecanesulfinic acid, octadecansulfinic acid, benzylsulfinic acid, 4-methylbenzylsulfinic acid, 4-chlorobenzylsulfinic acid, cyclohexylsulfinsulfonic acid, 2-chlorobenzene acid, benzene , 2-methylbenzenesulfinic acid, 4-ethylbenzenesulfinic acid, 4-methoxybenzenesulfinic acid, 4-ethoxybenzenesulfinic acid and 4-acetylaminobenzenesulfinic acid. Among these sulfinic acids, 4-methylbenzenesulfinic acid is particularly preferred. The reaction can be carried out at a temperature of 20-100 ° C, the preferred temperature range is 20-40 ° C.
Ein Verfahren zur Herstellung von Sulfinaten der 4,4'-Diaminobenzhydrole durch Umsetzung dieser Hydrole mit Sulfinsäuren ist bereits bekannt (US-Patent 3193404). Bei diesem Verfahren wird das Sulfinat durch Eingiessen der Kondensationslösung in kaltes Wasser oder in kalte Ammoniumhydroxidlösung gefällt, abgesaugt und mit Wasser gewaschen. Nach diesem Verfahren erhält man nur dann technisch brauchbare Sulfinate, wenn man von sehr reinem Diaminobenzhydrol ausgeht. Das übliche Verfahren zur Herstellung von Michlers Hydrol (4,4'-Tetramethyldiaminobenzhydrol) besteht in der Oxidation von 4,4'-Tetramethyldiaminodiphenylmethan mit Bleidioxid. Bei diesem Verfahren entstehen dunkel gefärbte Nebenprodukte, die sich in Eisessig lösen und beim Verdünnen mit Wasser zusammen mit dem Sulfinat ausfallen und diesem einen dunklen, unansehnlichen Farbton geben. Überraschenderweise wurde nun gefunden, dass, wenn man die Verdünnung der Kondensationslösung ausschliesslich mit organischen Lösungsmitteln vornimmt, diese Verunreinigungen in Lösung gehalten werden und ein Sulfinat abgeschieden wird, das sich ohne weitere Reinigung zur Herstellung von farblosen Kopierpapieren verwenden lässt. Das Arbeiten mit wasserhaltigen organischen Lösungsmitteln bis zu einem Wassergehalt von etwa 5% führt bereits zu merklich dunkleren Produkten, die jedoch noch technisch verwendbar sind. Lösungsmittel mit einem Wassergehalt von über 5% führen zu einer Farbzahl von 7 nach der Jodskala und sind nicht mehr geeignet zur Herstellung von farblosen Kopierpapieren.A process for the preparation of sulfinates of 4,4'-diaminobenzhydrols by reacting these hydrolyses with sulfinic acids is already known (US Pat. No. 3,193,404). In this process, the sulfinate is precipitated by pouring the condensation solution into cold water or cold ammonium hydroxide solution, suction filtered and washed with water. According to this process, technically usable sulfinates are only obtained when starting from very pure diaminobenzhydrol. The common process for making Michler's hydrol (4,4'-tetramethyldiaminobenzhydrol) is to oxidize 4,4'-tetramethyldiaminodiphenylmethane with lead dioxide. This process produces dark-colored by-products, which dissolve in glacial acetic acid and, when diluted with water, precipitate together with the sulfinate and give it a dark, unsightly shade. Surprisingly, it has now been found that if the condensation solution is diluted exclusively with organic solvents, these impurities are kept in solution and a sulfinate is deposited which can be used without further purification to produce colorless copy papers. Working with water-containing organic solvents up to a water content of about 5% already leads to noticeably darker products, which, however, can still be used industrially. Solvents with a water content of more than 5% lead to a color number of 7 according to the iodine scale and are no longer suitable for the production of colorless copy papers.
170 g Michlers Hydrol (4,4'-Tetramethyldiaminobenzhydrol), technische Qualität erhalten durch Oxidation von 4,4'-Tetramethyldiaminodiphenylmethan mit Bleidioxid, werden in 700 g Eisessig bei Raumtemperatur gelöst. Zu der dunkelblauen Lösung gibt man 101,5 g p-toluolsulfinsaures Natrium. Nach 5 Min. beginnt die Kristallisation von PTSMH (p-Toluolsulfinat des Michlers Hydrol). Man verdünnt nun mit 240 g Alkohol, lässt die Kristallsuspension 4 Std. bei Raumtemperatur rühren, saugt sie ab und wäscht das Reaktionsprodukt mit 400 g Alkohol in kleinen Portionen, bis die Kristalle eine helle Farbe angenommen haben. Ausbeute: 181,4 g; Schmelzpunkt: 192-194°C; Farbzahl einer 2,5%igen Lösung in Dibutylphthalat: 2-4.170 g of Michler's hydrol (4,4'-tetramethyldiaminobenzhydrol), technical quality obtained by oxidation of 4,4'-tetramethyldiaminodiphenylmethane with lead dioxide, are dissolved in 700 g of glacial acetic acid at room temperature. 101.5 g of sodium p-toluenesulfinate are added to the dark blue solution. After 5 minutes, the crystallization of PTSMH (p-toluenesulfinate from Michlers Hydrol) begins. It is then diluted with 240 g of alcohol, the crystal suspension is left to stir for 4 hours at room temperature, filtered off with suction and the reaction product is washed with 400 g of alcohol in small portions until the crystals have a light color. Yield: 181.4 g; Melting point: 192-194 ° C; Color number of a 2.5% solution in dibutyl phthalate: 2-4.
Setzt man anstelle von Äthanol eines der folgenden Lösungsmittel der Kondensationslösung zu und verfährt sonst in gleicher Weise, so erhält man das p-Toluolsulfinat des Michlers Hydrol ebenfalls in sehr guter Qualität und Ausbeute. Geeignete Lösungsmittel sind: Methanol, Isopropanol, Äthylenglykol, Methylglykol, Äthylglykol, Butylglykol, Methylglykolacetat, Äthylenglykoldiacetat, Äthylenglykoldimethyläther, Äthylenglykoldiäthyläther, Diäthylenglykoldimethyläther, Dioxan, Tetrahydrofuran und Acetonitril.If one of the following solvents is added to the condensation solution instead of ethanol and the procedure is otherwise the same, the p-toluenesulfinate from Michlers Hydrol is also obtained in very good quality and yield. Suitable solvents are: methanol, isopropanol, ethylene glycol, methyl glycol, ethyl glycol, butyl glycol, methyl glycol acetate, ethylene glycol diacetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dioxane, tetrahydrofuran and acetonitrile.
85 g Michlers Hydrol werden in einem Gemisch von 350 ml Propionsäire ind 150 ml Alkohol gelöst und anschliessend mit 50,8 g p-toluolsulfinsaurem Natrium versetzt. Die Temperatur steigt bis 31 °C an und das p-Toluolsulfinat des Michlers Hydrol kristallisiert aus. Nach 4stündigem Rühren bei Raumtemperatur saugt man das Reaktionsprodukt ab und wäscht es mit 300 ml Alkohol in kleinen Portionen, bis das Filtrat hell abläuft. Ausbeute: 90,4g; Schmelzpunkt: 188-190°C. Verwendet man anstelle der Propionsäure die gleiche Menge Äthoxyessigsäure und verfährt sonst in gleicher Weise, so erhält man ebenfalls das p-Toluolsulfinat des Michlers Hydrol in guter Ausbeute und Qualität.85 g of Michler's hydrol are dissolved in a mixture of 350 ml of propionic acid and 150 ml of alcohol, and 50.8 g of sodium p-toluenesulfinate are then added. The temperature is rising to 31 ° C and the p-toluenesulfinate from Michler's hydrol crystallizes. After 4 hours of stirring at room temperature, the reaction product is suctioned off and washed with 300 ml of alcohol in small portions until the filtrate runs off brightly. Yield: 90.4g; Melting point: 188-190 ° C. If the same amount of ethoxyacetic acid is used instead of the propionic acid and the procedure is otherwise the same, the p-toluenesulfinate from Michlers Hydrol is also obtained in good yield and quality.
85 g Michlers Hydrol werden in einem Gemisch von 200 ml Glykolsäure und 150 ml Alkohol gelöst und 50,8 g p-toluolsulfinsaures Natrium zugesetzt. Nach 4stündigem Rühren bei Raumtemperatur saugt man das Reaktionsprodukt ab und wäscht es in kleinen Portionen mit insgesamt 300 ml Alkohol. Ausbeute: 100,9 g; Schmelzpunkt: 182-186 °C.85 g of Michler's hydrol are dissolved in a mixture of 200 ml of glycolic acid and 150 ml of alcohol and 50.8 g of sodium p-toluenesulfinate are added. After stirring for 4 hours at room temperature, the reaction product is suctioned off and washed in small portions with a total of 300 ml of alcohol. Yield: 100.9 g; Melting point: 182-186 ° C.
Mit gleich gutem Resultat kann man anstelle der Glykolsäure auch Milchsäure verwenden.Lactic acid can be used instead of glycolic acid with the same good result.
85 g Michlers Hydrol werden in einem Gemisch von 50 ml Ameisensäure und 200 ml Äthanol gelöst und 50,8 g p-toluolsulfinsaures Natrium zugegeben. Nach 10 Min. kristallisiert das Sulfinat des Michlers Hydrol aus. Man lässt die Suspension 4 Std. bei Raumtemperatur rühren, saugt sie ab und wäscht das Reaktionsprodukt in kleinen Portionen mit 400 ml Alkohol, bis das Filtrat hell ist, dann noch mit 0,5 I einer 1%igen wässrigen Natriumsulfinatlösung.85 g of Michler's hydrol are dissolved in a mixture of 50 ml of formic acid and 200 ml of ethanol and 50.8 g of sodium p-toluenesulfinate are added. After 10 minutes the sulfinate of Michler's hydrol crystallizes out. The suspension is allowed to stir for 4 hours at room temperature, is filtered off with suction and the reaction product is washed in small portions with 400 ml of alcohol until the filtrate is light, then with 0.5 l of a 1% aqueous sodium sulfinate solution.
Ausbeute: 101,1 g; Schmelzpunkt: 189-193°CYield: 101.1 g; Melting point: 189-193 ° C
40 g Michlers Hydrol werden in 190 ml Eisessig gelöst. Die Lösung wird mit 15,5 g methansulfinsaurem Natrium versetzt. Nach 15 Min. kristallisiert das Methansulfinat des Michlers Hydrol aus. Man verdünnt die Suspension mit 100 ml Methanol, lässt noch 3 Std. nachrühren und saugt das Reaktionsprodukt ab. Man erhält 40,4 g Methansulfinat. Schmelzpunkt: 171-172°C. Eine Probe umkristallisiert aus Methylglykolacetat schmilzt bei 182-183°C.40 g of Michler's hydrol are dissolved in 190 ml of glacial acetic acid. 15.5 g of sodium methanesulfinate are added to the solution. After 15 minutes, the methane sulfinate from Michler's Hydrol crystallizes out. The suspension is diluted with 100 ml of methanol, the mixture is stirred for a further 3 hours and the reaction product is filtered off with suction. 40.4 g of methanesulfinate are obtained. Melting point: 171-172 ° C. A sample recrystallized from methyl glycol acetate melts at 182-183 ° C.
170 g Michlers Hydrol werden in 700 ml Eisessig bei Raumtemperatur gelöst und 104 g benzolsulfinsaures Natrium zugegeben. Nach wenigen Minuten kristallisiert das Benzolsulfinat des Michlers Hydrol aus. Man verdünnt die Suspension mit 200 ml Alkohol, lässt noch 4 Std. bei Raumtemperatur rühren und saugt das Reaktionsprodukt ab. Man wäscht es zunächst mit 500 ml Alkohol in kleinen Portionen und dann mit 1 I Wasser, in dem 20 g Natriumbicarbonat gelöst wurden. Nach Trocknen im Vakuum erhält man 192 g Benzolsulfinat des Michlers Hydrol, Schmelzpunkt 209-211°C.170 g of Michler's hydrol are dissolved in 700 ml of glacial acetic acid at room temperature and 104 g of sodium benzenesulfinate are added. After a few minutes, the Michlers Hydrol's benzenesulfinate crystallized out. The suspension is diluted with 200 ml of alcohol, stirred for a further 4 hours at room temperature and the reaction product is filtered off with suction. It is washed first with 500 ml of alcohol in small portions and then with 1 liter of water in which 20 g of sodium bicarbonate have been dissolved. After drying in vacuo, 192 g of benzenesulfinate from Michlers Hydrol, melting point 209-211 ° C.
Setzt man anstelle des benzolsulfinsauren Natriums 146,4 g 4-chlorbenzolsulfinsaures Natrium ein und verfährt sonst in gleicher Weise, so erhält man 216,1 g 4-Chlorbenzolsulfinat des Michlers Hydrol, Schmelzpunkt 197-198°C.If 146.4 g of sodium 4-chlorobenzenesulfinate are used instead of the sodium benzenesulfinate and the procedure is otherwise the same, 216.1 g of 4-chlorobenzenesulfinate from Michler's Hydrol, melting point 197-198 ° C.
65,2 g 4,4'-Tetraäthyldiaminobenzhydrol werden in 150 ml Eisessig und 100 ml Alkohol gelöst. Zu dieser Lösung gibt man 32,4 g p-toluolsulfinsaures Natrium. Unter Temperaturanstieg auf 35°C kristallisiert langsam das p-Toluolsulfinat des Tetraäthyldiaminobenzhydrols aus. Man lässt 22 Std. bei Raumtemperatur nachrühren, saugt das Reaktionsprodukt ab und wäscht es in kleinen Portionen mit 150 ml Alkohol, bis das Filtrat hell abläuft und dann mit 500 ml einer 1%igen wässrigen Lösung von p-toluolsulfinsaurem Natrium. Nach Trocknen im Vakuum erhält man 61,1 g p-Toluolsulfinat des 4,4'-Tetraäthyldiaminobenzhydrols, Schmelzpunkt 146-148°C.65.2 g of 4,4'-tetraethyldiaminobenzhydrol are dissolved in 150 ml of glacial acetic acid and 100 ml of alcohol. 32.4 g of sodium p-toluenesulfinate are added to this solution. As the temperature rose to 35 ° C., the p-toluenesulfinate of the tetraethyldiaminobenzhydrol slowly crystallized out. The mixture is left to stir for 22 hours at room temperature, the reaction product is filtered off and washed in small portions with 150 ml of alcohol until the filtrate runs off brightly and then with 500 ml of a 1% aqueous solution of p-toluenesulfinic sodium. After drying in vacuo, 61.1 g of p-toluenesulfinate of 4,4'-tetraethyldiaminobenz hydrol, melting point 146-148 ° C.
Ersetzt man das 4,4'-Tetraäthyldiaminobenzhydrol in diesem Beispiel durch eines der nachfolgend aufgeführten Hydrole und verfährt sonst in gleicher Weise, so erhält man ebenfalls die Sulfinate dieser Hydrole in guter Ausbeute und Qualität.If you replace the 4,4'-tetraethyldiaminobenzhydrol in this example with one of the hydroles listed below and otherwise proceed in the same way, the sulfinates of these hydrols are also obtained in good yield and quality.
Geeignete Hydrole sind: 4,4'-Tetramethyldiami- no-2,2'-dimethoxybenzhydrol, 4,4'-Tetramethyl- diamino-2,2'-dimethylbenzhydrol, 4,4'-Bisbenzylmethylaminobenzhydrol, 4,4'-Bisbenzyläthylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4'-Bisphenyläthylaminobenzhydrol, 4,4'-Bis- äthyloxäthylaminobenzhydrol,4,4'-Bischloräthyl- äthylaminobenzhydrol, 4,4'-Bispiperidinobenzhydrol, 4,4'-Bismorpholinobenzhydrol, 4,4'-Bis-N-methylpiperazinobenzhydrol, Bis-(N-methyl-6-tetrahydrochinolyl)-methan.Suitable hydroles are: 4,4'-tetramethyldiamino-2,2'-dimethoxybenzhydrol, 4,4'-tetramethyl-diamino-2,2'-dimethylbenzhydrol, 4,4'-bisbenzylmethylaminobenzhydrol, 4,4'-bisbenzylethylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4 '-Bisphenyläthylaminobenzhydrol, 4,4' -bis- äthyloxäthylaminobenzhydrol, 4,4'-Bischloräthyl- äthylaminobenzhydrol, 4,4'-Bispiperidinobenzhydrol, 4,4 ' -Bismorpholinobenzhydrol, 4,4 ' -Bis-N-methylpiperazinobenzhydrol, bis- (N-methyl-6-tetrahydroquinolyl) -methane.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782820486 DE2820486A1 (en) | 1978-05-10 | 1978-05-10 | PROCESS FOR THE PRODUCTION OF SULFINATES OF 4,4'DIAMINOBENZHYDROL AND ITS SUBSTITUTIONAL PRODUCTS |
| DE2820486 | 1978-05-10 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0005251A2 EP0005251A2 (en) | 1979-11-14 |
| EP0005251A3 EP0005251A3 (en) | 1979-12-12 |
| EP0005251B1 true EP0005251B1 (en) | 1981-01-07 |
Family
ID=6039051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79101293A Expired EP0005251B1 (en) | 1978-05-10 | 1979-04-30 | Process for the preparation of sulfinates of 4,4'-diaminobenzhydrol and of its substituted products, and copying paper containing these compounds |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0005251B1 (en) |
| JP (1) | JPS54148762A (en) |
| DE (2) | DE2820486A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4348330A (en) * | 1980-03-14 | 1982-09-07 | Ciba-Geigy Corporation | Process for the production of sulphinates of benzhydrol compounds |
| DE3337296A1 (en) * | 1983-10-13 | 1985-04-25 | Bayer Ag, 5090 Leverkusen | THERMOREACTIVE RECORDING MATERIAL, ITS PRODUCTION AND THE USE OF ACID-MODIFIED POLYMERISATS AS ACCEPTORS IN THIS RECORDING MATERIAL |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3193404A (en) * | 1959-03-19 | 1965-07-06 | Davis Chester | Associated dye salts and method of forming colored indicia therewith |
| DE2208611A1 (en) * | 1972-02-24 | 1973-09-06 | Basf Ag | METHOD OF MANUFACTURING ARYLECKY CLIP ON 4,4'-BIS (DIALKYLAMINO) BENZHYDRYL RECTANGULAR CLIP ON -SULPHONES |
-
1978
- 1978-05-10 DE DE19782820486 patent/DE2820486A1/en not_active Withdrawn
-
1979
- 1979-04-30 EP EP79101293A patent/EP0005251B1/en not_active Expired
- 1979-04-30 DE DE7979101293T patent/DE2960119D1/en not_active Expired
- 1979-05-08 JP JP5536979A patent/JPS54148762A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5735911B2 (en) | 1982-07-31 |
| EP0005251A2 (en) | 1979-11-14 |
| EP0005251A3 (en) | 1979-12-12 |
| JPS54148762A (en) | 1979-11-21 |
| DE2820486A1 (en) | 1979-11-15 |
| DE2960119D1 (en) | 1981-02-26 |
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